Hydrocarbon oil composition



3,017,362 HY DROCARBON OIL COMPOSITION Henryk A. Cyba, Chicago, Ill.,assiguor, by mesne assignments, to Universal. Oil Products Company, DesPiaines, 111., a corporation of Delaware No Drawing. Filed June 12,.1958, Ser. No. 741,463 14 Claims. (Cl. 252'51.5)

This invention relates to a novel additive for hydrocarbon oil and moreparticularly to a novel method of improving hydrocarbon oil in a numberof important properties.

During processing, transportation, storage and/or use, hydrocarbon oilsgenerally deteriorate, particularly when subjected to elevatedtemperature. For example, hydrocarbon oil being subjected tofractionation or conversion is first heated to an elevated temperature.Such heating may be effected in an externally fired furnace or it may beaccomplished by heat exchange with a hotter fluid. In the first case,the hydrocarbon fluid is passed through tubes during such heating and,in many cases, deposit formation occurs in the tubes and results in lossof efficient heating and/ or plugging of the furnace tubes. In heatexchange systems the hydrocarbon oil is pxssed either through tubesdisposed in a shell or through the shell surrounding the tubes. Duringheating of the oil, deposit formation occurs either within the tubes orin the hotter sections of the shell, with the result of decreasedefiiciency in heat transfer and even in plugging of the tubes. Anotherexample in which hydrocarbon oil is passed in heat exchange is in thecase of jet fuel, where the jet fuel is passed in heat exchange wtih thehot exhaust gases, both to cool the exhaust gases and to heat theincoming fuel. Temperatures as high as 500 F. or more are encounteredfor at least short periods of time, with the result that depositformation occurs and either plugs the heat exchanger or interferes witheflicient heat transfer.

Other examples where instability of the hydrocarbon oil is a problem arehydrocarbon oils heavier than gasoline including diesel oil, heateroils, burner oils, range oils, fuel oils, transformer oils, hydraulicoils, sloshing oils, etc. Deposit formation in these oils isobjectionable because it results in plugging of filters, strainers,burner tips, injectors, etc., reduction in viscosity and accordingly inflowing properties, as well as the formation of varnish and sludge inthe diesel engine. In addition to preventing these objectionable depositformations, the novel additive of the present invention also functionsto retard corrosion of metal surfaces in contact with hydrocarbon oiland water. It is well known that water generally is present inhydrocarbon oils and results in corrosion of piping, pumps, shells,fractionat-ors, receivers, storage tanks, etc., as well as internalequipment such as baflle plates, bubble trays, bubble caps, etc.

In addition to serving the important functions hereinbefore set forth,the novel additive of the present invention also serves to lower thepour point of the hydrocarbon oil. This is of advantage in the case ofheavier oils which are being pumped and also of particular advantage inthe case of lubricating oils, gas turbine oils, steam turbine oils, jetturbine oils, marine oils, etc. in order that the oil retain its flowingproperties at lower temperatures. In addition to reducing pour point andlowering the cold test, the additive also improves the viscosity indexof lubricating oil.

The additive of the present invention also serves an important functionin the case of gasoline or naphtha. As hereinbefore set forth, theadditive serves as a corrosion inhibitor and therefore reduces corrosionproblems during handling of the gasoline.

The additive also serves to improve hydrocarbon oils in anotherimportant manner. In many instances hydroi o p i United tates atent O3,017,362 Patented Jan. 16, 1962 carbon oil must meet Water tolerancespecifications. According to these specifications, a mixture ofisooctaneor jet fuel, water and the additive is shaken for a short period of timeand then allowed to stand for a given time. After this time there mustbe a clear break in order for the oil to pass this test. As will beshown in the appended example, the additive of the present invention isespecially advantageous in permitting the hYdIOCaIbOIl oil to pass thistest.

From the above description it will be noted that the novel additive ofthe present invention serves to improve hydrocarbon oil in a number ofdifferent ways. The hydrocarbon oil includes gasoline, naphtha, jetfuel, kerosene, burner oil, heater oil, range oil, gas oil, fuel oil,lubricating oil, residual oil, etc. As hereinbefore set forth, theadditive may be incorporated in the oil prior to heating for furtherprocessing, or it may be incorporated in the oil after such treatment.

In one embodiment the present invention relates to a method of improvinga hydrocarbon oil which comprises incorporating therein a stabilizingconcentration of an ester of a carboxylic acid and the condensationproduct of an epihalohydrin compound with an amine compound having atleast 12 carbon atoms.

In a specific embodiment the present invention relates to a method ofpreventing deposit formation in a heat exchanger through which twofluids at different temperatures are passed which comprisesincorporating in at least one of s id fluids, in an amount suflicient toprevent deposit formation, an ester of oleic acid and the condensationproduct of epichlorohydrin with'an amine compound having from about 12to about 40 carbon atoms per molecule.

In still another embodiment the present invention relates to a method ofimproving burner oil which comprises incorporating therein a stabilizingconcentration of an ester of the reaction product of terpene-maleicanhydride and the condensation product of epichlorohydrin and tallowamine.

In still another embodiment the present invention relates to hydrocarbonoil containing a stabilizing concentration of the novel additive hereinset forth.

The" novel additives of the present invention also are new compositionsof matter and are being so claimed in the present application.

As hereinbefore set forth, the novel additive of the present inventionis an ester of a carboxylic acid and the condensation product of anepihalohydrin compound with an amine compound having at least 12 carbonatoms. The amine compound used in preparing the condensation productcontains at least 12 carbon atoms and preferably at least 15 carbonatoms. Generally the total number of carbon atoms in the amine will notexceed about 40 carbon atoms per molecule. In a preferred embodiment theamine contains a straight chain of at least 3 carbon atoms attached tothe nitrogen atom. In this preferred embodiment, the alkyl groupattached to the nitrogen atom is of normal configuration and notsecondary, tertiary or of cyclic configuration. However, the alkyl groupmay contain branching in the chain, provided such branching occurs onthe fourth carbon atom froin the nitrogen atom or further distanttherefrom.

Any suitable alkyl amine meeting the requirements set forth herein maybe used in preparing the additive of the present invention. In additionto the above requirements, it is essnetial that the alkyl amine is aprimary or secondary amine; that is, only one or two of the hydrogenatoms attached to the nitrogen atom are substituted by alkyl groups.Tertiary amines (no hydrogen atom attached to the nitrogen atom) cannotbe used in the present invention. It is understood that the term alkylamine is used in the present specifications and claims to includeprimary alkyl amines, secondary alkyl amines, polyamines, N-alkylpolyamines, N,N-diall yl polyamines, etc., all of which meet therequirements hereinbefore set forth.

Illustrative examples of primary alkyl amines include dodecyl amine,tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecyl amine,heptadecyl amine, octadecyl amine, nonadecyl amine, eicosyl amine,heneicosyl amine, docosyl amine, tricosyl amine, tetracosyl amine,pentacosyl amine, hexacosyl amine, heptacosyl amine, octacosyl amine,nonacosyl amine, triacontyl amine, hentriacontyl amine, dotriacontylamine, tritriacontyl amine, tetratriacontyl amine, pentatriacontylamine, hexatriacontylamine, heptatriac ontyl amine, octatriacontylamine,

nonatriacontyl amine, tetracontyl amine, etc. Conveniently the longchain amines are prepared from fatty acids or more particularly frommixtures of fatty acids formed as products or by-products. Such mixturesare available commercially, generally at lower prices and, as anotheradvantage of the present invention, the mixtures may be used without thenecessity of separating individual amines in pure state.

An example of such a mixture is hydrogenated tallow amine which isavailable under various trade names including Alamine H26D and ArmeenHTD. These products comprise mixtures predominating in alkyl aminescontaining 6 to 18 carbon atoms per alkyl group, although they contain asmall amount of alkyl groups having 14 carbon atoms, and also meet theother requirements hereinbefore set forth.

Illustrative examples of secondary amines include di- (dodecyl) amine,di-(tridecyl) amine, di-(tetradecyl) amine, di-(pentadecyl) amine,di-(hexadecyl) amine, di- (heptade'cyl) amine, di-(octadecyl) amine,di-(nonadecyl) amine, di-(eicosyl) amine, etc. In another embodiment,which is not necessarily equivalent, the secondary amine will containone alkyl group having at least 12 carbon atoms and another alkyl grouphaving less than 12 carlion atoms, both of the alkyl groups having astraight chain of at least 3 carbon atoms attached to the nitrogen atom.Illustrative examples of such compounds include N-propyl-dodecyl amine,N-butyl-dodecyl amine, N-

amyl-dodecyl amine, N-butyl-tridecyl amine, N-amyl-tridecyl amine, etc.Here again, mixtures of secondary amines are available commercially,usually at a lower price, and such mixtures may be used in accordancewith the present invention, provided that the amines meet therequirements hereinbefore set forth. An example of such a mixtureavailable commercially in Armeen 2HT which consists primarily ofdioctadecyl amine and di- 7 hexadecyl amine.

.contyl-1,3-diaminopropane, N-octatriacontyl-l,3-diaminopropane,N-nonatriacontyl-l,3-diaminopropane, N-tetraco ntyl-1,3-diaminopropane,etc. As before, mixtures are available commercially, usually at lowerprices, of suitdominating in 12 to 14 carbon atoms each. Still anotherill example is N-soya-l,3-diaminopropane which predominates in alkylgroups containing 18 carbon atoms per group, although it contains asmall amount of alkyl groups having 16 carbon atoms.

While the N-alkyl-1,3-diaminopropanes are preferred compounds of thisclass, it is understood that s'uit'able alkyl ethylene diamines,N-alkyl-l,3-diaminobutanes, N- alkyl-1,4-diaminobutanes, N-alkyl-l,3-diaminopentanes, N-

alkyl-l,4-diaminopentanes, N alkyl-1,S-diaminopentanes,N-alkyl-1,3-diaminohexanes, N-alkyl-1,4-diaminohexanes,N-alkyl-1,5-diaminohexanes, N-alkyl-1,6-diaminohexanes, etc. may beemployed but not necessarily with equivalent results. Also, it isunderstood that polyamines containing 3 or more nitrogen atoms may beemployed provided they meet the requirements hereinbefore set forth.Illustrative examples of such compounds include N-dodecyldiethylenetriamine, N-tridecyl-diethylene triamine, N-tetradecyl-diethylenetriamine, etc., N-dodecyl-dipropylene triamine, N-tridecyl-dipropylenetriamine, N-tetradecyldipropylene triamine, etc., N-dodecyl-dibutylenetriamine, N-tridecyl-dibutylene triamine, N-tetradecyl-dibutylenetriamine, etc., N-dodecyl-triethylene tetramine, N-tridecyltriethylenetetramine, N-tetradecyl-triethylene tetramine, etc.,N-dodecyl-tripropylene tetramine, N-tridecyl-tripropylene tetramine,N-tetradecyl-tripropylene tetramine, etc., N-dodecyl-tributylenetetramine, N-tridecyl-tributylene tetramine, N-tetra-decyl-tributylenetetramine, etc., N-dodecyl-tetraethylene pentamine,N-tridecyl-tetraethylene pentamine, N-tetradecyl-tetraethylenepentamine, etc., N-do-' decyl-tetrapropylene pentamine,N-tridecyl-tetrapropylene pentamine, N-tetradecyl-tetrapropylenepentamine, etc., N-dodecyl-tetrabutylene. pentamine,N-tridecyl-tetrabutylene pentamine, N-tetradecyl-tetrabutylenepentamine, etc.

In another embodiment, polyaminoalkanes meeting the requirementshereinbefore set forth, may be employed but generally such materials arenot available commercially and, therefore, generally are not preferred.Illustrative examples of such compounds include l,l2-diarninododec ane,1,13-diaminotridecane, 1,14-diaminotetradecane, etc.

In general, it is preferred that the amine compound is a saturatedcompound and does not contain double bonds in the chain. However, insome cases, unsaturated compounds may be employed, provided they meetthe other requirements hereinbefore set forth, although not necessarilywith equivalent results. ,Such amine compounds may be prepared fromunsaturated fatty acids and, therefore, may be available commercially atlower cost. Illustrative examples of such amine compounds includedodecylenic amine, didodecylenic amine, N-dodecylenic ethylene diamine,N-dodecylenic-1,3-diaminopropane, oleic amine, dioleic amine, N-oleicethylene diamine, N-oleic- 1,3-diamino-propane, linoleic amine,dilinoleic amine,

N-linoleic ethylene diamine, N-linoleic-1,3-diaminopropane, etc. It isunderstood that these amine compounds are included in the presentspecifications and claims by reference to amine or amine compounds.

In another embodiment of the invention, two different amines may bereacted with the epihalohydrin compound. At least one of the amines mustmeet the quali fications hereinbefore set forth. The other amine maycomprise any suitable compound containing primary and/ or secondaryamine groups. Preferred compounds comprise ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, etc., similarpropylene and polypropylene polyamines, butylene and polyibiia butylenepolyainines, etc. In still another embodiment, other suitablenitrogen-containing compounds may be used as, for example, urea,monoethanol amine, etc.

As hereinbefore set forth, the amine compound is re acted with anepihalohydrin compound. Epichlorohydrin is preferred. Otherepichlorohydrin compounds include 1,2-epi-4-chlorobu-tane,2,3-epi-4-chlorobutane, 1,2-epi-- chloropentane,2,3-epi-5-chloropen-tane, etc. In general, the chloro derivatives arepreferred, although it is understood that the corresponding bromo andiodo compounds may be employed. In some cases epidihalohydrin compoundsmay be utilized. It is understood that the different epihalohydrincompounds are. not necessarily equivalent in the same or differentsubstrate and that, as hereinbefore set forth, epichlorohydrin ispreferred.

In general, 1 or 2 mols of amine compound are reacted with l or 2 molsof epihalohydrin compound. It is understood that, in some cases, anexcess of amine or of epihalohydrin may be supplied to the reaction Zonein order to insure complete reaction, the excess being removedsubsequently in any suitable manner. When 2 mols of amine are reactedper mol of epihalohydrin compound, the amine may comprise the same ordifferent amine compound.

In a preferred embodiment of the invention, the reaction of 1 mol ofamine compound with 1 mol of epihalohydrin compound proceeds to theformation of polymeric reaction product. In this embodiment of theinvention, the reaction is first effected at a temperature withintherange hereinafter set forth, with only a portion of the reactantsbeing present in the reaction mixture. After the initial reaction iscompleted, the remaining reactants are supplied to the reaction mixtureand the reaction is completed at a higher temperature but within thesame range set forth herein. For example, a portion of the amine may befirst reacted with the epihalohydrin and then the remaining portion ofthe amine is reacted. These polymers may contain from about 3 to about20 or more recurring units and preferably from about 5 to aboutrecurring units.

The desired quantity of alkyl amine and epihalohydrin compounds may besupplied to the reaction zone and therein reacted, although generally itis preferred to supply' one reactant to the reaction zone and thenintroduce the other reactant stepwise. Thus, usually it is preferred tosupply the amine to the reaction zone and to add the epihalohydrincompound step-wise, with stirring. When it is desired to react twodifferent alkyl amines with the epihalohydrin compound, theepihalohydrin compound is supplied to the reaction zone. One of theamines is added gradually, and the reaction completed,

followed by the addition of the second alkyl amine. Generally, it ispreferred to utilize a solvent and, in the preferred embodiment, asolution of the amine in a solvent and a separate solution of theepihalohydrin compound in a solvent are prepared, and these solutionsthen are commingled in the manner hereinbefore set forth. Any suitablesolvent may be employed, a particularly suitable solvent comprising analcohol including ethanol, propanol, butanol, etc, Z propanol beingparticularly desirable.

The reaction is effected at any suitable temperature,

which generally will be within the range of from about 20 to about 100C. and preferably is within the range of'from about 50 to about 75 C. Ahigher temperature rangeof from about 30 to about 150 C. or more, andpreferably of from about 50 toabout 100 C., is specified when thereaction is effected at superatmospheric pressure to increase thereaction velocity. Conveniently, this reaction is effected by heatingthe amine solution in dilute alcohol at refluxing conditions, withstirring, gradually adding the epihalohydrin compound thereto, andcontinuing the heating until the reaction is completed.

Either before or after removal of the reaction product from the reactionzone, the product is treated to remove halogen, generally in the form ofan inorganic halide salt as, for example, the hydrogen halide salt. Thismay be effected in any suitable manner and generally is accomplished byreacting the product with a strong inorganic base such as sodiumhydroxide, potassium hydroxide, etc., to form the corresponding metalhalide. The reaction to form the metal halide generally is effectedunder the same conditions as hereinbefore set forth. After this reactionis completed, the metal halide is removed in any suitable manner,including filtering, centrifugal separation, etc. It is understood thatthe reaction product also is heated sufiiciently to remove alcohol andwater and this may be effected either before or after the treatment toremove the inorganic halide.

In still another embodiment, after the reaction product of an alkylamine and epihalohydrin is prepared, the reaction product may be reactedwith other nitrogen-containing compounds including, for example, alkanolamines, urea, etc., instead of with the same or different alkyl amine ashereinbefore described. Illustrative alkanol amines include ethanolamine, propanol amine, butanol amine, pentanol amine, hexanol amine,etc.

As hereinbefore set forth, an ester of a carboxylic acid and thecondensation product prepared in the above manner is used as an additiveto hydrocarbon oil. Any suitable carboxylic acid may be used in formingthe ester and in one embodiment preferably comprises a. monobasiccarboxylic acid containing at least 6 carbon atoms, more particularlyfrom 6 to about 25 carbon atoms, and thus includes caproic, caprylic,lauric, myristic, palmitic, stearic, arachidic, behenic, lignoceric,cerotic, etc., decylenic, dodecylenic, palmitoleic, oleic, ricinoleic,petroselinic, vaccenic, linoleic, linolenic, eleostearic, licanic,parinaric, gadoleic, arachidonic, ceto'leic, erucic, selacholeic, etc.

However, in some cases, lower monobasic carboxylic acids may be employedand thus include formic, acetic, propionic, butyric, valeric,trimethylacetic, etc.

In another embodiment a polycarboxylic acid is used in forming the esterand preferably comprises a dibasic carboxylic acid containing at least 6and preferably at least 10 carbon atoms per molecule, and moreparticularly from about 20 to about 50 carbon atoms per molecule. Thepreferred acids are referred to herein as high molecular weightpolybasic carboxylic acids and include adipic, pimelic, suberic,azelaic, sebacic, phthalic, etc, aconitic, citric, etc., hemimellitic,trimesic, prehnitic, mellophanic, pyromellitic, mellitic, etc., andhigher molecular polybasic carboxylic acids. It is understood that amixture of acids may be employed.

A particularly preferred acid comprises a mixed byproduct acid beingmarketed commercially under the trade name of VR-l acid. This acid is amixture of polybasic acids, predominantly dibasic, has an averagemolecular weight by basic titration of about 750, an average molecularweight of about 1000, is a liquid at 77 F., has an acid number of aboutand iodine of about 36, and contains about 37 carbon atoms per molecule.

Another particularly preferred acid comprises a mixed acid beingmarketed commercially under the trade name of Empol 1022. This dimeracid is a dilinoleic acid and is represented by the following generalformula:

. least 6 carbon atoms per molecule are preferred. However, it isunderstood that dibasic acids containing less than 6 carbon atoms alsomay be employed in some cases and thus include oxalic, malonic,succinic, glutaric, etc.

In another embodiment, the carboxylic acid used in forming the ester isa reaction product of a terpene and an alpha,beta-unsaturated carboxylicacid or anhydride. Any suitable terpenic compound may be reacted withany suitable alpha-beta-unsaturated polycarboxylic acid or anhydride toform the reaction product for subsequent condensation with theepichlorohydrin-amine condensation product. In one embodiment a terpenehydrocarbon having the formula C H is employed, including alphapinene,beta-pinene, dipentane, d-limonene, l-limonene and terpinoline. Theseterpene hydrocarbons have boiling points ranging from about 150 to about185 C. In another embodiment the terpene may contain three double bondsin monomeric form, including terpene as allo-ocymene, o-cymene, myrcene,etc. Other terpenic compounds include alpha-terpinene, p-cymene, etc.

As hereinbefore set forth, the terpene is reacted with analpha,beta-unsaturated polycarboxylic acid or anhydride thereof. Anyunsaturated polycarboxylic acid having a point of unsaturation betweenthe alpha and beta carbon atoms may be employed. Illustrativeunsaturated dicarboxylic acids include m-aleic acid, fumaric acid,citraconic acid, mesaconic acid, aconitic acid, itaconic acid. While thedicarboxylic acids are preferred, it is understood that alpha,betaunsaturated polycarboxylic acids containing three, four or morecarboxylic acid groups may be employed. Furthermore, it is understoodthat a mixture of alpha-beta-unsaturated polycarboxylic acids andparticularly of alpha,beta-unsaturated dicarboxylic acids may be used.

While the alpha,beta-unsaturated polycarboxylic acid may be employed,advantages appear to be obtained in some cases when using the anhydridesthereof. Illustrative anhydrides include maleic anhydride, citraconicanhydride, aconitic anhydride, itaconic anhydride, etc. It is understoodthat a mixture of anhydrides may be employed and also that the anhydridemay contain substituents and particularly hydrocarbon groups attachedthereto.

The reaction of terpene and alpha,beta-unsaturated acid or anhydridegenerally is eflected at a temperature of from about 150 o about 300 C.,and preferably of from about 160 to about 200 C. The time of heatingwill depend upon the particular reactants and may range from 2 hours to24 hours or more. When desired, a suitable solvent may be utilized.Following the reaction, impurities or unreacted materials may be removedby vacuum distillation or otherwise, to leave a resinous 7 product whichmay be a viscous liquid or a solid.

A terpene-maleic anhydride reaction product is available commerciallyunder the trade name of Petrex acid. This acid is a stringy,yellow-amber colored mass and is mostly dibasic. It has an acid numberof approximately 530, a molecular weight of approximately 215 and asoftening point of 40-50 C.

While the aliphatic carboxylic acids generally are preferred, in somecases cyclic carboxylic acids may be employed. Aromatic carboxylic acidsinclude benzoic acid, toluic acid, etc., which acids also may containhydrocarbon and particularly alkyl substituents attached to the ring.Naphthenic carboxylic acids include cyclopentane carboxylic acid;cyclopentyl-acetic acid, methylcyclopentyl acid, camphonanic acid,cyclohexane carboxylic acid, methylcyclohexane carboxylic acid,dimethylcyclohexane carboxylic acid, trimethylcyclohexane carboxylicacid, etc.

It is understood that the various acids which may be used in preparingthe ester are not necessarily equivalent and also that mixtures of acidsmay be employed in preparing the esters. In some cases, in place of theacid, the anhydrides or certain esters of the acid may be utilized informing the ester with the condensation product of epihalohydrin-amine.These esters may contain up to about 8 carbon atoms in the ester groupbut preferably contain one or two carbon atoms. The ester portion mustbe volatile under the conditions of the esterification of theepihalohydrin-amine condensation product. In the esterification of thecondensation product, transesterification occurs; that is, the smallerester group is volatilized off and replaced by esterification of theepihalohydrinamine condensation product.

The ester of the carboxylic acid and epihalohydrinamine condensationproduct may comprise the partially or completely esterified product. Ashereinbefore set forth, the epihalohydrin-amine condensation product mayand preferably contains a number of recurring units, each of therecurring units having a hydroxyl group. Accordingly, it will be seenthat one, all or any number of the hydroxyl groups may be esterifiedwith the acid. Generally it is preferred to use stoichiometric amountsof these reactants in order to effect substantially completeesterification. One mol equivalent of carboxylic acid will be used pereach equivalent of hydroxyl group in the epihalohydrin-aminecondensation product.

The ester may be prepared in any suitable manner and, in general, isprepared readily by refluxing the acid and condensation product,preferably with the continuous removal of water formed in the reaction.The refluxing is continued until the theoretical amount of water iscollected and thus may range from 1 hour to 48 hours or more at atemperature above about C. Although the esterification may be effectedin the absence of a solvent, which generally will require the use ofvacuum, normally it is preferred to utilize a solvent. The exacttemperature or refluxing will depend upon the particular solventemployed. For example, with benzene as the solvent, the temperature willbe in the order of 80 C., with toluene the temperature will be in theorder of C., and with xylene in the order of -155 C. Other preferredsolvents include cumene, naphtha, decalin, etc. Any suitable amount ofthe solvent may be employed but preferably should not comprise a largeexcess because this will tend to lower the reaction temperature and slowthe reaction. Water formed during the reaction may be removed in anysuitable manner including, for example, by operating under reducedpressure, by removing an azeotrope of water-solvent, by distilling thecondensation product at an elevated temperature, etc. As hereinbeforeset forth, a higher temperature and solvent preferably are utilized ineffecting the reaction in order to remove the water as it is beingformed.

It is understood that the different esters which may be prepared andused in accordance with the present invention are not necessarilyequivalent. For example, one ester may be effective for a certainpurpose in one hydro carbon oil, while another ester may be efiective inthe same substrate for a different purpose or in difierent substratesfor the same or dififerent purposes.

The concentration of esters to be incorporated in the hydrocarbon oilwill depend upon the particular use. For example, when utilized toprevent heat exchanger deposits, the ester generally is used in aconcentration of from 1 to 1000 parts per million by weight of thehydrocarbon oil. When used for other purposes, the ester may be used ina concentration of from about 0.000l% to about 1% or more by weight ofthe hydrocarbon oil. It is understood that the ester is incorporated inthe hydrocarbon oil in any suitable manner and generally is effectedwith stirring in order to obtain intimate mixing thereof. However, whenintroduced in a flowing stream of .oil, mixing is accomplished byturbulence normally encountered therein.

As hereinbefore set forth, the ester is particularly advantageous foruse to prevent deposit formation in heat exchangers. Such heat exchangeis utilized, for example, in a hydrotreating process in which oil issubjected to hydrogen treating in the presence of a catalyst comprisingalumina-molybdenum oxide-cobalt oxide or aluminamolybdenumsulfide-cobalt sulfide. The oil, which may comprise gasoline, kerosene,gas oil or mixtures thereof, is introduced into the process at atemperature of from about ambient to 200 F. and is passed in heatexchange with reactor eflluent products being withdrawn at a temperatureof from about 500 to about 800 F. The charge is heated by such heatexchange to a temperature of from about 300 to about 600 F., then isheated in a furnace or otherwise to a temperature of from about 625 toabout 800 F. and passed with hydrogen in contact with the catalyst. Thistreatment serves to remove impurities and to hydrogen-ate unsaturatescontained in the charge. Another illustration is a reforming process inwhich gasoline is contacted with hydrogen in the presence of aplatinum-containing catalyst at a temperature of from about 700 to about1000 F. and the hot efliuent product from the reaction Zone is passed incontact with the charge in order to cool the former and heat the latter.

An example in which oil is subjected to fractionation and the charge ispassed in heat exchange with the hot effluent products is in a crudecolumn. In this column, crude oil is subjected to distillation at atemperature of from about 600 to about 700 F. in order to remove lightercomponents as overhead and/or side streams. In some cases the chargefirst is passedin heat exchange with the overhead and/or side streamsfrom this column and then is passed in heat exchange with the hotterproducts withdrawn from the bottom of the crude column. In this way thecharge is progressively heated and the hotter products are cooled.

The above examples are illustrative of typical uses of heat exchange toeffect economies in the process. However, difiiculty is experienced inthe heat exchange due to deposit formation, with the consequentnecessity of interrupting plant operation as hereinbefo-re set forth. In

accordance with the present invention, deposit formation in heatexchanger is reduced to an extent that normal plant operation need notbe interrupted for this reason.

It is understood that the advantages of the present invention may beobtained in any suitable heat exchange equipment. In general, thisequipment comprises a series of tubes or a tube coil positioned within ashell. One of the fluids is passed through the tubes, while the otherfluid is passed through the shell. The heat exchange equipment generallyis positioned externally to a fractionator or reactor. However, in somecases, the heat exchanger takes the form of a reboiler or condenser, andeither a tube coil or a shell containing tubes is positioned within thelower or upper portion of the fractionator or reactor.

When the ester of the present invention is added to a finished product,it is incorporated therein with suitable mixing, and may be used alongwith other additives to be added to the oil for specific reasons as, forexample, metal deactivator, antioxidant, synergist, cetane improver,etc. As hereinbefore set forth, the ester serves to improve the oil inmany ways including preventing deposition of sediment, preventingformation of varnish or sludge, preventing corrosion of metal surfaces,depressing pour point, etc. It is understood that all of theseimprovements are not necessarily obtained in all substrates with thesame additive. However, the ditierent Oils will be improved in one ormore ways as hereinbefore set forth.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same. 7

EXAMPLE I The ester of this example is the Z-ethylhexoic acid ester ofthe condensation product of epichlorohydrin and tallow amine. Thecondensation product was prepared by the reaction of equal molproportions of hydrogenated tallow amine (Armeen HTD) andepichlorohydrin. It will be noted that the tallow amine is a mixture ofprimary amines predominating in 16 to 18 carbon atoms per alkyl group.The reaction wa effected by first forming a solution of 2 mols ofepichlorohydrin in 600 cc. of a solvent mixture comprising 400 cc. ofxylene and 200 cc. of Z-propanol. A separate solution of 2 mols ofArmeen HTD was prepared in an equal volume of xylene. One mol of thelatter solution was added gradually to the ep-ichlorohydrin solution,with stirring and heating at 55-60 C. for a period of 2.5 hours. Thenanother mol of Armeen HTD was added gradually to the reaction mixture,stirred and reacted at C. for 2.5 hours. One mol of sodium hydroxidethen was added with stirring and heating at 90 C. for 3.5 hours, afterwhich another mol of sodium hydroxide was added and the mixture stirredand reacted at 85-90 C. for one hour. Following completion of thereaction, the mixture was cooled, filtered, and the filtrate then wasdistilled to remove the alcohol. The condensation prodnot was recoveredas a 50% by weight solution of active ingredient in xylene.

330 grams of the 50% solution of the condensation product prepared inthe above manner wa mixed with '75 grams of Z-ethylhexoic acid. Thecondensation product was used in a /2 equivalent of the hydroxyl groupsand the ethylhexoic acid was used in a concentration of /2 mol. Themixture was boiled under refluxing conditions for 24 hours. A total of20.8 cc. of water was collected. The xylene was removed by distillationon a steam bath under vacuum. The ester was recovered as a dark brown,free-flowing liquid and had an index of refraction 11 of 1.4693.

The ester prepared in the above manner was evaluated in a methodreferred to as the Erdco test. In this method heated oil is passedthrough a filter, and the time required to develop a pressuredifferential across the filter of 25 in./Hg is determined. It isapparent that the longer the time required to reach this differentialpressure, the more efiective is the additive.

The oil used in this example was a mixture of 76% range oil and 24%catalytically cracked cycle oil. When evaluated in the Erdco test usinga preheater temperature of 300 F. and a filter temperature of 350 F., asample of the oil not containing an additive developed 25 in./ Hgpressure within 35 minutes. On the other hand, another sample of the oilcontaining 0.000l% by weight of the ester described above and evaluatedin the same manner developed a differential pressure of only 0.5 in./Hgafter 180 minutes. It will be seen that this low concentration ofadditive was effective in considerably reducing filter plugging.

EXAMPLE II The ester of this example was prepared using a mixed fattyacid which is available in the open market as Neo- Fat l855 and contains49% stearic acid, 48% palmitic acid and 3% oleic acid. It is apparentthat the resultant product is a mixed ester. However, it also isapparent that these mixed acids are available commercially at a lowerprice than the pure acids. As another important feature of the presentinvention, these mixed acids are used to prepare the ester without theadditional cost otherwise required to separate and recover the pureacid.

grams of a condensation product (50% solution in xylene) prepared in themanner described in Example I is commingled with 67 grams of the mixedacid. The condensation product is used in a concentration of 4equivalent of the hydroxyl groups and the mixed acid is used in aconcentration equivalent to 4 mol. The mixture was boiled at refluxingconditions (temperature l50l55 C.) for 16 hours. 8 cc. of Water wascollected. Xylene was removed by distillation on a steam bath undervacuum. The ester was recovered as an amber, brittle solid, having amelting point of 48-53 C.,

1 1 and is readily soluble in hydrocarbon oil at slightly elevatedtemperature.

The ester prepared in the above manner was evaluated in the Erdco testusing another sample of the oil described in Example I. The preheatertemperature was 300 F. and the filter temperature was 350 P. 0.0005 byweight of the ester prepared in the above manner was incorporated intoanother sample of the oil described in Example I, and developed adifferential pressure of only 0.1 in./Hg after 180 minutes. This is tobe compared to the 25 in./Hg pressure developed in 35 minutes when usingthe oil without additive. Here again it will be noted that the additiveof the present invention was effec- EXAMPLEIII' I The ester of thisexample was prepared using a mixed acid available commercially asNee-Fat 94-04. This mixed acid comprises 80% oleic acid, linoleic acid,5% stearic acid, 4% palmitic acid and 1% linolenic acid. As mentionedbefore, it is an important advantage of the present invention that thesemixed acids are used satisfactorily to prepare effective additiveswithout the additional cost otherwise necessary to separatesubstantially pure acids.

163.1 grams of a condensation product (50% solution in xylene) preparedin the manner described in Example I was commingled with 70.5 grams ofthe mixed acid described above, together with 100 grams of xylene, andthe mixture was refluxed at 148 C. The condensation product was used ina concentration of equivalent based on hydroxyl content and the mixedacid was used in a concentration of mol. Following completion of thereaction, the product was heated to 170 C. under water pump vacuum toremove the xylene. The product was recovered as a grainy solid whichbecame fluid at temperatures aove 80 F. It had a basic nitrogen contentof 1.54 meq./ g. and an acid number of 0.38 meq./1g. The index ofrefraction n is 1.4785.

The ester prepared in the above manner was used as a pour pointdepressant in lubricating oil, which lubricating oil was a commercialS.A.E. Mid-Continent solvent extracted oil. This oil, without additive,had an ASTM cold test of 5 F. and an ASTM pour point of 10 F. 1% byweight of the ester prepared in the above manner was incorporated in asample of this lubricating oil and served to reduce the ASTM cold testto --5 F. and the ASTM pour point to 0 F.

EXAMPLE IV The ester prepared as described in Example II also wasevaluated in the Erdco test. In this run a commercial J.P.6 jet fuel wasused and accordingly was evaluated at a higher temperature. This isbecause jet fuels normally encounter higher temperatures. during use. Inthis run the preheater is at a temperature of 400 F. and the filter at atemperature of 500 F. Furthermore, the particular jet fuel used in thisrun was extremely difficult to benefit by an additive. Severalcommercially available and normally eflective experimental additiveswere evaluated in this jet fuel and were of no benefit. Accordingly, theimproved results obtained with the ester of this example is evidence ofthe unusual effectiveness of this additive.

The J .P.-6 jet fuel without additive developed a differential pressureof in./Hg within 117 hours. 0.005 by weight of the ester described inExample III was incorporated in another sample of this fuel, and thefuel developed a differential pressure of only 0.65 in./Hg after 300minutes.

The ester also was evaluated according to the C.F.R. fuel coker thermalstability test. In this test, the oil heated to the specifiedtemperature is passed through the annular space surrounding a heatedinside tube of 17" length and A" diameter positioned within an outsidetube of 95 inside diameter. The inside tube is heated by means of aheating coil positioned therein to a temperature of either 300 or 400 F.depending upon the particular fuel being evaluated. The test isconducted for 300 minutes, at a pressure of pounds per square inch, anda flow rate of 6 pounds of fuel per hour. Following the run theequipment is dismantled, 13" or less of the inner tube is marked off in1" increments and the deposits on the outside surface of the heatedinner tube are rated by visual comparison with standard metal coupons.In general the rating is substantially as follows:

0--c1ean and bright 1--metal dulled but not discolored 2-light yellowdiscoloration 3--'-yell'ow to tan discoloration 4-anything darker orheavier than 3 The ratings for the individual 1" increments are addedtogether to give a final tube rating. Military specifications for jetfuels require that none of the 1 increments rates poorer than 3.

In this example, the jet fuel was evaluated at 400 F. A sample of thefuel without additive had a tube rating of 28. Another sample of thefuel containing 0.005% by weight of the ester of this example had a fuelrating of 18. As hereinbefore set forth, this is an exceptionally goodresult in view of the fact that a number of other additives were ofsubstantially no benefit when run in this jet fuel.

EXAMPLE V The ester of this example was prepared using a mixed acidavailable commercially as Aliphat 44-A and is derived from tall oil.This is a mixture of about 47% oleic acid and about 47% linoleic acid.

209 grams of a condensation product (50% solution in xylene) prepared inthe manner described in Example I was commingled with 96.3 grams of themixed acid. The condensation product was used in a concentration of /3equivalent based on hydroxyl content and the mixed acid was used in aconcentration of /3 mol. The mixture was boiled under refluxingconditions for 9 hours, during which time a total of 10.2 cc. of waterwas collected. The xylene was removed by distilling at C. under waterpump vacuum. The ester was recovered as a solid gel.

The ester prepared in the above manner also was evaluated by the fuelcoker thermal stability test described in Example IV in another sampleof the J.P.6 jet fuel also described in that example.

0.005 by weight of the ester of this example was incorporated in anothersample of the jet fuel and, when evaluated in the above manner, had afuel rating of 19. This is to be compared with the fuel rating of 28obtained in the absence of the additive. As mentioned in Example IV,this result is exceptionally good in view of the difficulty inbenefiting this particular jet fuel with an additive.

EXAMPLE VI The ester of this example was prepared using a mixed tall oilderived acid available commercially as Crofatol #1 and contains about51% oleic acid and about 46% linoleic acid. This ester was prepared insubstantially the same manner as described in Example V. The ester wasrecovered as a viscous dark brown liquid and had an index of refraction11 of 1.4807.

The ester prepared in the above manner was evaluated as a pour pointdepressant in lubricating oil. The lubricating oil was a commercialS.A.E. 20 Mid-Continent solvent extracted oil which, without additive,had an ASTM cold test of 5 F. and an ASTM pour point of 10 F. 1% byweight of the ester prepared in the above manner was incorporated in asample of this lubricating oil and served to reduce the ASTM cold testto -10 F. and the ASTM pour point to -5 F. It will be noted that thisadditive was effective as a pour point depressant.

13 EXAMPLE vn An ester prepared in substantially the same manner asdescribed in Example III was evaluated as a lubricating oil additive andtested in a Lauson engine operated at high oil temperature (280 F.) andlow jacket temperature (210 F.). A typical commercial parafiinicsolventextracted lubricating oil was used.

1% by weight of the ester was incorporated in the lubricating oil. Inaddition, 0.5% by weight of a diaminodiphenyl ether antioxidant also wasincorporated in the oil. For comparison purposes, the following tablereports the results when using a sample of the oil without additive andalso another sample of the oil containing only the diaminodiphenyl etherantioxidant.

Oil ring plugging, percent. Slndgez In crank case Used Oil:

Neutralization N o Pentane Insoluble Viscosity at 100 F Viscosity at 210I 1.

1 CR photos as guide, =c1ean, 0=dirty.

From the data in the above table, it will be noted that the additive ofthe present invention considerably improved the lubricating oil. Thehigh piston rating was maintained in spite of the considerable drop whenusing the diaminodiphenyl ether antioxidant alone. The ring plugging wasreduced to zero. The sludge in the crank case was clean, in contrast tothe dirty crank case obtained when using the diaminodiphenyl etherantioxidant alone. The bearing weight loss, oil consumption and used oilneutralization number were all considerably improved. It is particularlynotable that the pentane insoluble and viscosity of the used oil wasconsiderably improved as compared to the oil without additive.

EXAMPLE VIII The ester of this example is a caprylic acid ester of acondensation product (50% solution in xylene) prepared in substantiallythe same manner as described in Example I. As hereinbefore set forth,economic advantages accrue to the use of mixed acids availablecommercially. Accordingly, the caprylic acid used in this example isavailable commercially as Neo-Fat 8 and comprises 93% caprylic acid, 4%capric acid-and 3% caproic acid. 224.7 grams of the 50% activeingredient solution in xylene of the condensation product was commingledwith 48.7 grams of the mixed acid. The condensation product was used ina concentration equivalent to /3 of the hydroxyl content and the acidwas used in a concentration of /3 mol. The mixture was refluxed for 16hours and a total of 11.4 cc. of water was collected. The xylene wasremoved by distilling at 155 C. under water pump vacuum. The ester wasrecovered as a viscous brown oil having an index of refraction n of1.4702. It was readily soluble in a concentration of 50% in lubricatingoil.

EXAMPLE I):

The ester of this example is a capric ester of a condensation productprepared in substantially the same manner as described in Example I.Here again a commercially available mixed acid was used. This acid isavailable commercially as Nee-Fat l0 and comprises 92% capric acid, 5%lauric acid and 3% caprylic acid. This ester was prepared substantiallyin the same manner as described in Example VIII. A total of 11.3 cc. ofwater was collected. The product is a dark brown gel which becomes fluidwhen heated to F. or higher. The ester had an index of refraction n of1.4704.

EXAMPLE X The ester of this example is a coco ester of a condensationproduct prepared as described in Example I. The mixed acid used in thispreparation is available cornmercially as Nee-Fat 255 and contains 57%lauric acid, 21% myristic acid, 10% palmitic acid, 7% oleic acid, 3%linoleic acid and 2% stearicacid. 224.7 grams of the condensationproduct (50% solution in xylene) were refluxed with 69.5 grams of thecoco acid for 16 hours, and the xylene later removed by distilling at C.under water pump vacuum. The product was recovered as an amber coloredwaxy solid which was soluble in lubricating oil up to 50% by weightconcentration.

EXAMPLE XI The ester of this example is an isodecanoic acid este of acondensation product prepared in the manner described in Example I. 326grams of the condensation product (50% solution in xylene) were mixedwith 79.5 grams of the isodecanoic acid and the mixture was refluxed for16 hours. The ester was recovered as a free flowing dark brown oilhaving an index of refraction :1 of 1.4710.

EXAMPLE XII The ester of this example is a naphthenic acid ester of acondensation product prepared as described in Example I. The naphthenicacid is a commercially available mixture. 209.6 grams of thecondensation product (50% solution in xylene) were refluxed with 75.8grams of the naphthenic acid for 16 hours. A total of 10 cc. of waterwas collected. The Xylene was removed by distillation at 195 C. underwater pump vacuum. The ester was recovered as a dark brown viscousliquid which was soluble in a concentration of 50% by weight inlubricating oil.

EXAMPLE x111 The ester of this example is an oleic acid ester of acondensation product prepared as described in Example I. 200 grams ofthe condensation product (50% solution in xylene), 83.4 grams of oleicacid and cc. of xylene were refluxed in a Dean-Stark water trap. 4.5 cc.of water was recovered. The resultant mixture was blended withadditional xylene to a total weight of 358.6 grams, thereby giving a 50%by weight active ingredient solution.

As hereinbefore set forth, the additive of the present invention servesto permit hydrocarbon oils to pass the water tolerance test. Accordingto this test as specified in MILI25017, 20 ml. of a buffered ordistilled water is placed in a 100 ml. glass stoppered graduatedcylinder, and 80 ml. of isooctane containing the additive is commingledwith the water. The cylinder is shaken for 2 minutes and allowed tostand undisturbed for 5 minutes. The interface then is inspected for anysigns of emulsion, scum or foreign matter.

The ester prepared in this example was added in a concentration ofgreater than 200 parts per million to 15 EXAMPLE XIV The ester of thisexample is a Petrex acid ester of a condensation product prepared asdescribed in Example I. As hereinbefore set forth, Petrex acid isprimarily a dibasic acid having an acid number of approximately 530 anda molecular weight of 215. Here again, this is a mixed acid availablecommercially at lower cost and accordingly advantageously is used in thepresent invention. 400 grams of the condensation product (50% solutionin xylene), 62 grams of Petrex acid (equivalent weight of 104) and 110cc. of Xylene were refluxed overnight. 4 cc. of water was recovered. Theresultant mixture was blended with ylene to a total weight of 524 grams,thereby giving a final solution of 50% by weight of active ingredient.

The ester prepared in the above manner was evaluated according to a testused to rate diesel fuels and fuel oils. In this test 50 cc. of the oilto be tested is placed in a 150 ml. beaker and then heated to 300 F. for90 minutes. The beaker is allowed to cool to room temperature and thecontents are filtered through filter paper. The paper then is dried andused for rating the fuel. In order to pass this test, the fuelcontaining the additive must give no more increase in color on the paperthan is obtained by carrying out the test with a standard sample of thefuel. The discoloration then is evaluated by determining thereflectance.

The diesel oil used in this test is a blend of 30% range oil and 70%catalytic cycle stock. A control sample of the fuel, before heating,gave a reflectance reading of 97 which, however, after heating asdescribed above, rated only 29. 80 parts per million of the esterprepared as described above and parts per million of a commercial copperdeactivator were incorporated in another sample of this fuel. Whenevaluated in this test, the oil containing the additives gave areflectance reading of 84. The copper deactivator was added in a smallconcentration in order to simulate commercial practice which is to alsoadd a copper deactivator to the fuel. From the above data, it will beseen that the ester of the present invention was effective in permittingthe oil to pass the diesel oil stability test.

I claim as my invention:

1. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an ester of a carboxylic acid of "from about 6 to about 50 carbonatoms per molecule and the condensation product of from 1 to 2 mols ofan epihalohydrin compound with from 1 to 2 mols of an aliphatic aminehaving from about 12 to about 40 carbon atoms per molecule, saidepihalohydrin compound being selected from the group consisting ofepichlorohydrin, 1,2- cpi-4-chlorobutane, 2,3-epi-4-chlorobutane,1,2-epi-5-chloropentane, 2,3-epi-5-chloropentane and corresponding bromoand iodo compounds, the amount of said acid being sufficient to esterifyfrom one to all of the hydroxyl groups in said condensation product.

2. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an ester of stoichiometric amounts of a monobasic carboxylic acidcontaining from about 6 to about 25 carbon atoms per molecule and thecondensation product of from 1 to 2 mols of epichlorohydrin with from 1to 2 mols of an alkyl amine having from .about 12 to about 40 carbonatoms per molecule.

3. Hydrocarbon oil containing from about 0.0001% 710 about 1% by weightof an ester of stoichiometric :amounts of a dibasic carboxylic acidcontaining from .about 6 to about 50 carbon atoms per molecule and thecondensation product of from 1 to 2 mols of epichlorohy- -.drin withfrom 1 to 2 mols of an alkyl amine having from ;about 12 to about 40carbon atoms per molecule.

'4. Hydrocarbon oil containing from about 0.000l% to ;about 1% by weightof an .ester of stochiometric amounts @Q a naph henic a id and thecondensation product of 16 from 1 to 2 mols of epichlorohydrin with from1 to 2 mols of an alkyl amine having from about 12 to about 40 carbonatoms per molecule.

5. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an oleic acid ester of the condensation product of equimolar amountsof epichlorohydrin and tallow amine, the ester being formed from one molequivalent of acid per each equivalent of hydroxyl group in thecondensation product.

6. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof a stearic acid ester of the condensation product of equimolar amountsof epichlorohydrin and tallow amine, the ester being formed from one molequivalent of acid per each equivalent of hydroxyl group in thecondensation product.

7. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof a Z-ethylhexoic acid ester of the condensation product of equimolaramounts of epichlorohydrin and tallow amine, the ester being formed fromone mol equivalent of acid per each equivalent of hydroxyl group in thecondensation product.

8. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an ester of stoichiometric amounts of a terpene-maleic anhydridereaction product and the condensation product of equimolar amounts ofepichlorohydrin and tallow amine.

9. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an ester of a naphthenic acid and the condensation product of from 1to 2 mols of epichlorohydrin with from 1 to 2 mols of tallow amine, theester being formed from one mol equivalent of acid per each equivalentof hydroxyl group in the condensation product.

10. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an ester of a carboxylic acid of from about 6 to about 50 carbonatoms per molecule and the condensation product, formed at a temperaturefrom about 20 C. to about C., of from 1 to 2 mols of an aliphatic aminecontaining from about 12 to about 40 carbon atoms per molecule with from1 to 2 mols of an epihalohydrin compound selected from the groupconsisting of epichlorohydrin, 1,2-epi-4-chlorobutane,2,3-epi-4-chlorobutane, 1,2-epi-5-chloropentane, 2,3-epi-S-chloropentane and corresponding bromo and iodo compounds, theamount of said acid being suflicient to esterify from one to all of thehydroxyl groups in said condensation product.

11. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an ester of stoichiometric amounts of a carboxylic acid of from about6 to about 50 carbon atoms per molecule and the condensation product,formed at a temperature of from about 20 C. to about 150 C., ofequimolar amounts of epichlorohydrin and an alkyl amine of from about 12to about 40 carbon atoms per molecule.

12. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an ester of a carboxylic acid of from about 6 to about 50 carbonatoms per molecule and the condensation product, formed at a temperatureof from about 20 C. to about 150 C., of equimolar amounts ofepichlorohydrin and tallow amine, the ester being formed from one molequivalent of acid per each equivalent of hydroxyl group in thecondensation product.

13. The hydrocarbon oil composition of claim 12 further characterized inthat said acid is a fatty acid.

14. The hydrocarbon oil composition of claim 12 further characterized inthat said acid is a naphthenic acid.

Jacob Apr. 10, 1934 Kritchevsky Aug. 10, 1937 (Other references onfollowing page) 17 UNITED STATES PATENTS Schlack Jan. 10, 1939 FreemanFeb. 13, 1940 Schoeller et a1. Sept. 10, 1940 Dietrich Dec. 24, 1940 518 Bock et a1. Nov. 23, 1948 Zinzalian Jan. 23, 19-51 Banes et a1. Nov.24, 1953 Shen et a1. Sept. 30, 1958 Dougherty Oct. 13, 1959

1. HYDROCARBON OIL CONTAINING FROM ABOUT 0.0001% TO ABOUT 1% BY WEIGHTOF AN ESTER OF A CARBOXYLIC ACID OF SFROM ABOUT 6 TO ABOUT 50 CARBONSATOMS PER MOLECULE AND THE CONDENSATION PRODUCT OF FROM 1 TO 2 MOLS OFAN EPIHALOHYDRIN COMPOUND WITH FROM 1 TO 2 MOLS OF AN ALIPHATIC AMINEHAVING FROM ABOUT 12 JTO ABOUT 40 CARBON ATOMS PER MOLECULE, SAIDEPIHALOHYDRIN COMPOUND BEING SELECTED FROM THE GROUP CONSISTIG OFEPICHLOROHYDRIN, 1,2EPI-4-CHLOROBUTANE, 2,3-EPI-4-CHLOROBUTANE,1,2-EPI-5-CHLOROPENTANE, 2,3-EPI-5-CHLOROPENTANE AND CORRESPONDING BROMOAND IODO COMPOUNDS, THE AMOUNT OF SAID ACID BEING SUFFICIENT TO ESTERIFYFROM ONE TO ALL OF THE HYDROXYL GROUPS IN SAID CONDENSATION PRODUCT.